TW201435135A - Metal amide deposition precursors and their stabilization with an inert ampoule liner - Google Patents

Abstract

Described are methods and apparatuses for the stabilization of precursors, which can be used for the deposition of manganese-containing films. Certain methods and apparatus relate to lined ampoules and/or 2-electron donor ligands.

Description

Metal amide deposition precursor and stabilization of the precursor with an inert ampere lining

Embodiments of the invention relate generally to thin film deposition. More specifically, embodiments of the present invention relate to stabilization of precursors during a thin film deposition process.

Integrated circuits have evolved into complex devices that can include millions of transistors, capacitors, and resistors on a single wafer. The development of wafer design continues to require faster circuits and greater circuit density, and faster circuits and greater circuit densities require more and more precise manufacturing processes. Precise processing of the substrate requires precise control of the temperature, rate and pressure in the transfer of the fluid used during processing.

Chemical vapor deposition (CVD) and atomic layer deposition (ALD) are two deposition processes for forming or depositing a variety of materials on a substrate. In general, CVD and ALD processes involve the delivery of gaseous reactants to the surface of the substrate at the temperature and pressure conditions that favor the thermodynamics of the reaction, on the surface of the substrate. A chemical reaction takes place.

Many of these deposition processes use a heated vessel or canister (such as an ampoule or a bubbler) that contains a volatile liquid precursor under conditions that aid in vaporizing the precursor. Despite this, a common problem with the deposition of thin films is that many precursors have limited stability within the ampoule. This is especially the case with metal precursors with low coordination numbers, as metal centers are more susceptible to attack with other compounds. The complex can react with impurities, decomposition products or even the metal surface of the ampoule itself. The yield of the deposition tool is reduced without increasing the stability of the precursor, or worse, the process conditions may need to be completely redesigned to inhibit decomposition and/or adverse reactions. Therefore, additional equipment and methods for stabilizing metal precursors are needed.

One aspect of the invention pertains to an apparatus for generating a chemical precursor gas. The apparatus includes: a can having a side wall, a top end and a bottom forming an internal volume; an intake port and an outlet port, the intake port and the outlet port being in fluid communication with the internal volume; the liner being located on the side wall, the top end or At least a portion of the bottom portion, wherein the liner comprises an inert metal oxide; and a precursor, the precursor being located in an interior volume of the can, wherein the precursor comprises at least one Mn-N bond and a 2-electron donor ligand . In one or more embodiments, the liner is on at least a portion of the bottom. In some embodiments, the inert metal oxide comprises a dielectric. In one or more embodiments, the inert metal oxide comprises SiO ₂ , Al ₂ O ₃ , TiO ₂ , lanthanum carbide, lanthanum oxychloride or Ta ₂ O ₅ . In some embodiments, the 2-electron donor ligand comprises pyridine, tetrahydrofuran or tetrahydrothiophene, tetramethylethylenediamine, acetonitrile, a tertiary amine, or 2,2'-bipyridine. In one or more embodiments, the precursor has a structure that is expressed as:

Another aspect of the invention is directed to a method of depositing a manganese-containing film. The method comprises the steps of: providing a precursor comprising at least one Mn-N bond; and flowing the precursor through a device for generating a chemical precursor gas, wherein the device has a liner comprising an inert metal oxide. In one or more embodiments, the inert metal oxide comprises a dielectric. In some embodiments, the inert metal oxide comprises SiO ₂ , Al ₂ O ₃ , TiO ₂ , tantalum carbide, tantalum carbonoxide or Ta ₂ O ₅ . In one or more embodiments, the precursor has a structure that is expressed as: Wherein each A is independently selected from carbon or hydrazine, and each R is independently selected from hydrogen, methyl, substituted or unsubstituted alkane, branched or unbranched alkane, substituted or unsubstituted olefin, branched or unbranched Alkenes, substituted or unsubstituted alkynes, branched or unbranched alkynes or substituted or unsubstituted aromatics.

In one or more embodiments, each A is 矽. In some embodiments, each R group is a methyl group. In one or more embodiments, the precursor comprises bis(bistrimethyldecyl)guanamine manganese. In some embodiments, the method further comprises the steps of: exposing the substrate surface to the bis (bis trimethyl silicon alkyl) Amides of NH ₃ containing manganese and second precursor. In one or more embodiments, the precursor further comprises a 2-electron donor ligand. In some embodiments, the 2-electron donor ligand comprises pyridine, tetrahydrofuran or tetrahydrothiophene, tetramethylethylenediamine, acetonitrile, a tertiary amine, or 2,2'-bipyridine. In one or more embodiments, at least the Mn-N bond is part of the 2-electron donor ligand. In some embodiments, the precursor has a structure that is represented as: In one or more embodiments, the method further includes exposing the surface of the substrate to the precursor.

Another aspect of the invention is directed to a method of depositing a manganese-containing film, the method comprising the steps of: exposing a surface of a substrate to the vaporized precursor, wherein the precursor comprises:

300‧‧‧ source cans

302‧‧‧ Carrier gas source

306‧‧‧Processing chamber

312‧‧‧ valve

314‧‧‧ valve

402‧‧‧Cylindrical side wall

404‧‧‧ Cover

406‧‧‧Intake 埠

408‧‧‧Exhaust gas

410‧‧ ‧ baffle

414‧‧‧Precursor materials

416‧‧‧Liquid

418‧‧‧ upper area

420‧‧‧ Shell

422‧‧‧Intake pipe

424‧‧‧ first end

426‧‧‧ second end

430‧‧‧Resistive heater

432‧‧‧ bottom

436A‧‧‧Disconnected parts

436B‧‧‧Disconnecting accessories

438‧‧‧ internal volume

444‧‧‧ lining

450‧‧‧ oil collector

452‧‧‧ oil collector body

454‧‧ ‧ baffle

456‧‧‧ center line

The above detailed description of the present invention, which is set forth in the <RTIgt; It is to be understood, however, that the appended claims

1 is a cross-sectional side view of an exemplary embodiment of an apparatus in accordance with one or more embodiments of the present invention; and FIG. 2 is a diagram illustrating a comparison of one or more embodiments in accordance with the present invention. Examples and percentages of non-volatile residues of three examples; Figure 3 is a graph showing the percentage of non-volatile residues in one of the comparative examples and three examples according to one or more embodiments of the present invention ; 4 graph Mn (TMSA) solution of ₂ wt thermal curves; 5 graph Mn (TMSA) ₂ (py) ₂ of the thermal gravimetric curve; and a sixth graph _{Mn (TMSA) 2 (TMEDA)} 2 of Pyrolysis weight curve.

Before the several exemplary embodiments of the invention are described, it is understood that the invention is not limited by the details of the construction or process steps set forth in the following description. The invention is capable of other embodiments and the invention may be

It has been discovered that the Mn precursor can be stabilized by modifying the ligand and/or modifying the means used during the thin film deposition process. As discussed above, the precursor can react with the inner wall of the ampoule, and the inner wall of the ampoule can be made, for example, of stainless steel. Nevertheless, the use of an inert metal oxide to add a lining to the inner wall of the ampoule can help prevent the reaction of the precursor. Alternatively, the precursor can be synthesized such that the precursor is coordinated to a guanamine ligand that also contains a 2-electron donor moiety, or a separate 2-electron donor ligand can be added to provide chemical stability. Sex. The apparatus and processes described herein assist in stabilizing metalorganic materials (i.e., precursors) that can undergo degradation at elevated temperatures.

Thus, aspects of the present invention provide enhanced stability that prevents degradation of the precursor during production runs. An increase in the stability of the precursor means that the yield of the deposition tool can be increased while completely avoiding having to redesign the process conditions.

device

One aspect of the invention pertains to an apparatus for generating a chemical precursor gas, which in some embodiments is referred to as an ampoule. The apparatus includes: a can having a side wall, a top end and a bottom forming an internal volume; an intake port and an outlet port, the intake port and the outlet port being in fluid communication with the internal volume; the liner being located on the side wall, the top end or At least a portion of the bottom portion, wherein the liner comprises an inert metal oxide; and a precursor, the precursor being located In the internal volume of the can, wherein the precursor comprises at least one Mn-N bond and a 2-electron donor ligand. In one or more embodiments, the liner is located on at least a portion of the bottom. In some embodiments, the device is an on-board reservoir containing metalorganic materials. In one or more embodiments, the apparatus includes a heating element to heat the precursors.

Variants of the device include different lining materials. For example, in some embodiments, the inert metal oxide comprises a dielectric. In other embodiments, the inert metal oxide comprises SiO ₂ , Al ₂ O ₃ , TiO ₂ , tantalum carbide, tantalum carbonoxide or Ta ₂ O ₅ . In one or more embodiments, the inert metal oxide is a decyl alkyl inert metal oxide.

In some embodiments, the 2-electron donor ligand is to help stabilize the ligand of the precursor. In some embodiments, the Mn-N bond is part of the 2-electron donor ligand. In one or more embodiments, the 2-electron donor ligand comprises pyridine (py), tetrahydrofuran (THF), tetrahydrothiophene, tetramethylethylenediamine (TMEDA) ligand, acetonitrile, tertiary amine Or 2,2'-bipyridyl. In some embodiments, the precursor contains a trimethyldecyl decylamine (TMSA) ligand. In other embodiments, the precursor has a structure that is expressed as:

The method described in Horvath et al., "Manganese(II)silylamides"("Manganese(II)silylamides" specifically describes the synthesis of Mn(TMSA) ₂ (THF)) can be synthesized as described herein. Precursor. MnCl ₂ and LiN(SiMe ₃ ) ₂ in THF were used to produce the precursor. This process can be applied to other ligands and use parallel processes.

It may be advantageous to add a liner to the ampoule because the inner surface of the ampoule may remain in contact with the deposition chemistry for a long period of time. Thus, in one or more embodiments, only the ampules of the deposition chamber system are lined. Although valves and wiring may not be in prolonged contact with deposition chemicals, in one or more embodiments of the invention, such valves and wiring may also be coated.

Figure 1 illustrates a cross-sectional view of one embodiment of such devices, or such devices are referred to as "source cans" 300 . The "source canister" 300 is typically coupled between the carrier gas source 302 and the processing chamber 306 . Source tank 300 typically includes an ampoule or other sealed container having a housing 420 suitable for storing precursor material 414 (e.g., Mn(TMSA) ₂ (py) ₂ ), and precursor material 414 via sublimation or vaporization process Process (or other) gases can be generated. Precursor material 414 comprises a precursor comprising at least one Mn-N bond and a 2-electron donor ligand. The outer casing 420 is typically made of a material that is substantially inert to the precursor material 414 and gases generated from the precursor material, and thus, the material of the construction can vary based on the gas to be produced.

Housing 420 can have any number of geometries. In the embodiment illustrated in FIG. 1, the outer casing 420 includes a cylindrical side wall 402 and a bottom portion 432 sealed by a cover 404 . The cover 404 can be coupled to the side wall 402 by soldering, bonding, adhesive or other sealing methods. Alternatively, a seal, O-ring, close gasket or the like may be placed at the junction between the side wall 402 and the cover 404 to prevent leakage from the source canister 300 . Side wall 402 may alternatively comprise other hollow geometries, such as hollow square tubes.

In accordance with one or more embodiments of the present invention, the apparatus of Figure 1 also has a lining 444 along the bottom 432 . The liner may comprise a dielectric or, in other embodiments, SiO ₂ , Al ₂ O ₃ , TiO ₂ , tantalum carbide, tantalum carbonoxide or Ta ₂ O ₅ .

Intake enthalation 406 and outlet enthalpy 408 are formed through the source tank to allow gas to flow into or out of source tank 300 . The crucibles 406 , 408 may be formed to pass through the cover 404 and/or the side walls 402 of the source canister 300 . The crucibles 406 , 408 are generally sealable to allow the interior of the source canister 300 to be isolated from the surrounding environment during removal of the source canister 300 from the gas delivery system (not shown). In an embodiment, the valves 312 , 314 are sealingly coupled to the crucibles 406 , 408 to prevent the source canister 300 from being removed from the gas delivery system when refilling the precursor material 414 or replacing the source canister 300 Leakage from the source tank 300 . Pairing disconnect fittings 436 A, 436 B can be coupled to valves 312 , 314 to facilitate removal of source canister 300 from gas delivery system 304 and displacement of source canister 300 to gas distribution system 304 . Valves 312 , 314 are typically ball valves or other reliable sealing valves that allow source tank 300 to be removed from the system, efficiently loaded and recirculated while filling, transferring or coupling source tank 300 to the gas delivery Potential leakage from source tank 300 is minimized during the system. Alternatively, the source canister 300 is refilled via a refill cartridge (not shown), such as a vial having a VCR fitting that is placed over the lid 404 of the source canister 300 . Precursor material 414 can be introduced into source tank 300 by removing cover 404 or via one of crucibles 406 , 408 .

Source tank 300 may include at least one baffle 410, an internal baffle 410 is disposed in an upper region 418 of the source tank 300. The baffle 410 is disposed between the intake enthalpy 406 and the bleed air enthalpy 408 to form an extended average flow path to prevent direct (ie, straight) flow of carrier gas from the intake enthalpy 406 to the bleed air enthalpy 408 . This has the effect of increasing the average residence time of the carrier gas in the source tank 300 and increasing the amount of sublimation or vaporized precursor gas carried by the carrier gas. In addition, the baffle 410 directs the carrier gas over the overall exposed surface of the precursor material 414 disposed in the source canister 300 to ensure repeatable gas generation characteristics and efficient consumption of the precursor material 414 . The number, spacing and shape of the baffles 410 can be selected to tune the source canister 300 for optimal generation of precursor gases. For example, a greater number of baffles 410 can be selected to impart a higher carrier gas velocity at the precursor material 414 , or the shape of the baffle 410 can be configured to control the consumption of the precursor material 414 to be more effective. The precursor material is used.

Intake manifold 422 may be disposed in interior volume 438 of source tank 300 , as appropriate. Tube 422 is coupled to intake port 406 of source canister 300 by first end 424 and terminates at second end 426 in upper region 418 of source canister 300 .

Optionally, the apparatus may contain an oil collector 450 because the agitation of the precursor material 414 may cause droplets to be entrained in the carrier gas and carried to the processing chamber 306 . To prevent droplets of liquid 416 from reaching the processing chamber 306 , the oil collector 450 can be coupled to the outlet port 408 of the source tank 300 , as appropriate. Oil collector 450 may include a body 452, body 452 includes a plurality of staggered baffles 454, such a plurality of baffles 454 extends beyond the centerline 452 oil collector body 456, and toward the source tank 300 is inclined downward slightly at least . The baffle 454 forces gas to the processing chamber 306 to flow around the baffle 454 along a tortuous path. The surface area of the baffle 454 provides a larger surface area exposed to the flowing gas that adheres to oil droplets that may be entrained in the gas. The downward slope of the baffle 454 allows any oil that accumulates in the oil collector to flow downward and back to the source tank 300 .

The precursor material 414 generates a precursor gas at a predetermined temperature and pressure. Gas sublimated or vaporized from the precursor material 414 may accumulate in the upper region 418 of the source tank 300 , and the gas may be purged by an inert carrier gas that enters through the inlet enthalpy 406 and flows out of the gas outlet 408 to It is transported to the processing chamber 306 . In one embodiment, the precursor material 414 is heated to a predetermined temperature by a resistive heater 430 disposed adjacent the sidewalls 402 . Alternatively, the precursor material 414 can be heated by other means, such as by a rake heater (not shown) disposed in the upper region 418 or the lower region 434 of the source can 300 , or by using a carrier gas. A heater (not shown) upstream of the intake port 406 preheats the carrier gas.

Deposition process

The equipment described herein can be used during the deposition of the manganese containing film. Accordingly, one aspect of the present invention is directed to a method of depositing a manganese-containing film using any of the apparatus described herein for generating a chemical precursor gas. The precursor contained in the interior of the device can be used as a source of manganese in the thin film deposition process. One or more embodiments relate to vaporizing the precursors described herein in the apparatus for generating a chemical precursor gas described herein. The surface of the substrate can then be exposed to the vaporized precursor. In one or more embodiments, the 2-electron donor ligand comprises a pyridine (py), tetrahydrofuran (THF), tetrahydrothiophene or tetramethylethylenediamine (TMEDA) ligand. In other embodiments, the precursor has a structure that is expressed as:

Another aspect of the invention is directed to a method of depositing a manganese-containing film, the method comprising the steps of: providing a precursor comprising at least one Mn-N bond; and flowing the precursor through an ampoule having an inertness Lining of metal oxide. The method can be part of any deposition process using an ampoule or other device for generating a chemical precursor gas. Thus, for example, the method can be part of chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma enhanced chemical vapor deposition (PECVD), plasma enhanced atomic layer deposition (PEALD), or other deposition processes. The processes described herein can be used to deposit a variety of manganese containing films including, but not limited to, MnN and films consisting essentially of manganese. Thus, in one or more embodiments, the method further comprises exposing the surface of the substrate to any of the precursors described herein.

Any variation of the apparatus described above can also be applied to the method. Thus, for example, in one or more embodiments, the inert metal oxide comprises a dielectric. In other embodiments, the inert metal oxide comprises SiO ₂ , Al ₂ O ₃ , TiO ₂ , tantalum carbide, tantalum carbonoxide or Ta ₂ O ₅ .

As mentioned above, the precursor comprises at least one Mn-N bond. In one or more embodiments, the precursor is any of the stabilized precursors described above. That is, in some embodiments, the precursor further comprises a 2-electron donor ligand, which itself may contain a Mn-N bond. In one or more embodiments, the 2-electron donor ligand is a ligand that helps stabilize the precursor. In some embodiments, the 2-electron donor ligand comprises a pyridine (py), tetrahydrofuran (THF), tetrahydrothiophene or tetramethylethylenediamine (TMEDA) ligand. In other embodiments, the precursor has a structure that is expressed as:

In some embodiments, the precursor has a structure that is represented as: Wherein each A is independently selected from carbon or hydrazine, and each R is independently selected from hydrogen, methyl, substituted or unsubstituted alkane, branched or unbranched alkane, substituted or unsubstituted olefin, branched or unbranched Alkenes, substituted or unsubstituted alkynes, branched or unbranched alkynes or substituted or unsubstituted aromatics. The oxidation state of manganese can be any suitable oxidation state that can react with the substrate or the second precursor. In some embodiments, the manganese is Mn(II) or Mn(III). In one or more embodiments, each A is 矽. In some embodiments, each R group is a methyl group. In other embodiments, the precursor comprises bis(bistrimethyldecyl)guanamine manganese, the bis(bistrimethyldecyl)guanamine manganese having a structure, the structure being expressed as:

The above precursors can be used to form manganese (Mn) or manganese nitride (MnN _x ) from organometallic precursors. The deposition methods may be atomic layer deposition (ALD) or chemical vapor deposition (CVD). The organometallic precursor can include a manganese sulfonium alkyl amide complex. The deposited manganese or MnN _x film can be used as an alternative diffusion barrier layer in back-end process copper interconnects to replace the currently used PVD TaN or ALD TaN. The deposition method can be integrated with ALD TaN deposition to produce manganese-doped TaN or MnN _x doped germanium. Other dopants can also be used. In one or more embodiments, the barrier layer comprises from 0.1% to 10% dopant based on the weight of the manganese layer. In some embodiments, the barrier layer comprises from 0.2% to 8% by weight of dopant. In a particular embodiment, the barrier layer comprises from 0.5% to 5% by weight of dopant.

In some embodiments, the substrate is exposed to the first precursor and the second precursor. Thus, in one or more embodiments, the method further comprises exposing the substrate surface to bis (bis trimethyl silicon group) of the step of second precursor Amides of NH ₃ and comprising manganese. Exposure to such precursors can be carried out substantially simultaneously (as in a CVD reaction) or sequentially (as in an ALD reaction). As used in this specification and the appended claims, the term "substantially simultaneously" means that the two precursor gases flow at least partially into the chamber (to react with each other) and co-flow toward the surface of the substrate. Those skilled in the art will appreciate that certain regions of the substrate may simply be exposed to one precursor until the other precursor diffuses into the same region.

In some embodiments, the Mn precursor may be used with one or more additional precursors. Examples include ammonia or hydrogen. Therefore, as an example, if ammonia is used, a manganese nitride thin film can be formed. Conversely, if hydrogen is used as the second precursor, it is possible to form a film consisting essentially of manganese.

In some embodiments, the manganese film comprises MnNx. The x of some embodiments is in the range of from about 0.1 to about 3, or in the range of from about 0.2 to about 2, or in the range of from about 0.25 to about 1. In some embodiments, the film comprises manganese ruthenate and the film can be formed over the dielectric layer. In one or more embodiments, the manganese film comprises manganese citrate when the manganese film is deposited near the surface of the dielectric, and the manganese film comprises manganese nitride when the manganese film is deposited away from the surface. The transition from citrate to nitride can be progressive or in discrete steps.

According to various embodiments of the invention, the film can be deposited substantially on any substrate material. As used herein, "substrate surface" refers to any substrate or material surface formed over a substrate upon which a thin film treatment is performed during the manufacturing process. For example, the surface of the substrate on which the processing can be performed includes, depending on the application, materials such as tantalum, niobium oxide, strain tantalum, silicon germanium (SOI), tantalum oxide doped with tantalum, tantalum nitride. Doped yttrium, ytterbium, gallium arsenide, glass, sapphire and any other Materials (such as metals, metal nitrides, metal alloys, and other conductive materials). The barrier layer, metal or metal nitride on the surface of the substrate comprises titanium, titanium nitride, tungsten nitride, tantalum and tantalum nitride, aluminum, copper or any other conductor or conductive or non-conductive resistive barrier for device fabrication. . The substrate can have a variety of sizes, such as 200 mm or 300 mm diameter wafers and rectangular or square panes. Substrates (embodiments to which the invention may be applied) include, but are not limited to, semiconductor wafers (such as crystalline germanium (eg, Si<100> or Si<111>), tantalum oxide, strained tantalum, niobium, doped Hetero- or undoped polysilicon, doped or undoped germanium wafers, III-V materials (such as GaAs, GaN, InP, etc.) and patterned or unpatterned wafers. The substrate can be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal, and/or bake the substrate surface.

Since embodiments of the present invention provide a method for depositing or forming a doped manganese-containing film, the processing chamber is configured to expose the substrate to a series of gases and/or plasmas during a vapor deposition process. The processing chamber will include a separate supply of reactants, and a supply of any carrier gas, purge gas, and inert gases such as argon and nitrogen, which are in fluid communication with the gas inlets for each reactant and gas. . Each inlet may be controlled by a suitable flow controller, such as a mass flow controller or a volumetric flow controller, in communication with a central processing unit (CPU) to allow each reactant to flow to the substrate to perform as herein Describe the deposition process. The central processing unit can be any form of computer processor that can be used to control multiple chambers and sub-processors in an industrial setting. The CPU can be coupled to the memory, and the CPU can be one or more easy to obtain memory, such as random access memory (RAM), read only memory (ROM), flash memory, compressed disc, floppy disk, Hard drive or any other form of local or Remote digital storage. The support circuit can be coupled to the CPU to support the CPU in a conventional manner. Such circuits include cache memory, power supplies, clock circuits, input/output circuitry, subsystems, and the like.

The co-reactant is typically in the form of a vapor or a gas. The reactants can be delivered using a carrier gas. The carrier gas, purge gas, deposition gas or other process gas may contain nitrogen, hydrogen, argon, helium, neon or a combination of the above. The various plasmas described herein (such as nitrogen plasma or inert gas plasma) may be ignited from the plasma co-reactant gas and/or may comprise a plasma co-reactant gas.

In one or more embodiments, a plurality of gases for the process can be pulsed through the inlet from a plurality of orifices or outlets, through the gas passages and into the central passage. In one or more embodiments, the deposition gas may be sequentially pulsed to the showerhead and passed through the showerhead. Alternatively, the gases may flow simultaneously through the gas supply nozzle or head and the substrate and/or gas supply head may be moved to sequentially expose the substrate to the gases.

In some embodiments, one or more layers may be formed during a plasma enhanced atomic layer deposition (PEALD) process. In some processes, the use of plasma provides sufficient energy to promote the material to an excited state where the surface reaction becomes favorable or suitable. Introducing the plasma into the process can be continuous or pulsed. In some embodiments, sequential pulses of precursor (or reactive gas) and plasma are used to treat a layer. In some embodiments, the reagent can be ionized via the native end (ie, inside the processing region) or ionized at the distal end (ie, outside of the processing region). In some embodiments, distal ionization can occur upstream of the deposition chamber such that ions or other high energy or luminescent materials are not in direct contact with the deposited film. In some PEALD processes, the plasma is external to the processing chamber. In, for example, by a remote plasma generator system. The plasma can be generated by any suitable plasma generation process or technique known to those skilled in the art. For example, the plasma can be generated by one or more microwave (MW) frequency generators or radio frequency (RF) generators. The frequency of the plasma can be tuned depending on the particular reactive species being used. Suitable frequencies include, but are not limited to, 2 MHz, 13.56 MHz, 40 MHz, 60 MHz, and 100 MHz. Although plasma may be used during the deposition process disclosed herein, it should be noted that such plasmas may not be required.

According to one or more embodiments, the substrate is subjected to processing before and/or after forming the layer. This process can be performed in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is moved from the first chamber to a separate second chamber for further processing. The substrate can be moved directly from the first chamber to the separate processing chamber, or the substrate can be moved from the first chamber to one or more transfer chambers and subsequently moved to the desired separate processing chamber. Thus, the processing device can include a plurality of chambers in communication with the transfer station. Such devices can be referred to as "cluster tools" or "cluster systems" and the like.

In general, a cluster tool is a modular system that includes a plurality of chambers that perform a variety of functions including substrate center exploration and orientation, degassing, annealing, deposition, and/or etching. According to one or more embodiments, the cluster tool includes at least one first chamber and one central transfer chamber. The central transfer chamber can house a robot that can move the substrate between the processing chamber and the load lock chamber and between the processing chambers and between the load lock chambers. The transfer chamber is typically maintained under vacuum and the transfer chamber provides an intermediate platform for reciprocating the substrate from one chamber to another and/or to the load lock chamber, the load lock chamber being positioned in the cluster The front end of the tool. Adapted it can be used for both the public present invention known cluster tools for Centura ^® and Endura ^®, Centura Endura ^{® ®,} and both can be purchased from the city of Santa Clara, California, Applied Materials. The details of such a grading vacuum substrate processing apparatus are disclosed in U.S. Patent No. 5,186,718, the entire disclosure of which is incorporated herein by reference. Nonetheless, the specific configuration and combination of chambers may be varied for the purpose of achieving the specific steps of performing the processes as described herein. Other processing chambers that may be used may include, but are not limited to, cyclic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning. , heat treatment (such as RTP), plasma nitriding, degassing, orientation, hydroxylation, and other substrate processes. By performing the process in a chamber on the cluster tool, surface contamination of the substrate and atmospheric impurities can be avoided, so that the substrate does not oxidize prior to deposition of the subsequent film.

According to one or more embodiments, the substrate is continuously under vacuum or "load lock" conditions, and the substrate is not exposed to ambient air as it moves from one chamber to the other. Thus, the transfer chambers are under vacuum conditions and the transfer chambers are "emptied" to vacuum pressure. An inert gas may be present in the processing chamber or transfer chamber. In some embodiments, an inert gas is used as the purge gas to remove some or all of the reactants after forming a layer on the surface of the substrate. According to one or more embodiments, a purge gas is injected into the outlet of the deposition chamber to prevent movement of reactants from the deposition chamber to the transfer chamber and/or additional processing chamber. Thus, the inert gas stream forms a barrier at the outlet of the chamber.

The substrate can be processed in a single substrate deposition chamber in which the deposition chamber A single substrate is loaded, processed, and unloaded prior to processing another substrate. The substrate can also be processed in a continuous manner, such as a conveyor belt system, in which a plurality of substrates are individually loaded into the first portion of the chamber, moved through the chamber, and unloaded from the second portion of the chamber . The shape of the chamber and associated conveyor system can form a straight path or a curved path. Additionally, the processing chamber can be a rotary transfer in which a plurality of substrates are moved about a central axis and exposed for deposition, etching, annealing, cleaning, etc., throughout the rotary transfer path.

The substrate can be heated or cooled during processing. This heating or cooling can be accomplished by any suitable means including, but not limited to, changing the temperature of the substrate support and flowing the heating or cooling gas to the surface of the substrate. In some embodiments, the substrate support includes a heater/cooler that can be controlled to conductively change the substrate temperature. In one or more embodiments, the gas (reaction gas or inert gas) employed may be heated or cooled to locally change the substrate temperature. In some embodiments, the heater/cooler is positioned within the chamber adjacent the substrate surface to convectively vary the substrate temperature.

The substrate can also be fixed or rotated during processing. The rotating substrate can be rotated continuously or in discrete steps. For example, the substrate can be rotated all the way through the entire process, or the substrate can be rotated a small amount between the steps of exposing the substrate to different reactive gases or purge gases. Rotating the substrate during processing (continuously or stepwise) can help result in more uniform deposition or etching by minimizing effects such as local variations in gas flow geometry.

In an atomic layer deposition type chamber, the substrate may be exposed to first or second precursors separated or temporally separated in the process space. Time ALD is Conventional processes in which a first precursor flows into a chamber to react with a surface. The first precursor is removed from the chamber prior to flowing the second precursor to the chamber. In space ALD, both the first precursor and the second precursor flow simultaneously to the chamber, but the two precursors are spatially separated to have an area between the gas streams that prevents such The precursor is mixed. In space ALD, the substrate must move relative to the gas distribution panel, or vice versa.

The "one or one embodiment", "some embodiments" or "one or more embodiments" referred to throughout the specification means that the particular features, structures, materials, or characteristics described in connection with the embodiments are included herein. In at least one embodiment of the invention. Therefore, terms such as "in one or more embodiments", "in some embodiments" or "one/an embodiment" are not necessarily representative of the present invention. The same embodiment. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

Although the invention is described herein with reference to the particular embodiments, it is understood that these embodiments are only illustrative of the principles and applications of the invention. It will be apparent to those skilled in the art that various modifications and changes can be made in the method and apparatus of the present invention without departing from the spirit and scope of the invention. Accordingly, the present invention is intended to cover such modifications and alternatives

Instance

First instance

According to the table below, two manganese precursors were placed in containers filled with stainless steel or SiO ₂ lining:

All samples were heated to a temperature of 90 ° C and maintained for a period of 18 days, and the percentage of non-volatile residue was measured at different time intervals over 18 days. One of the manganese precursors contains two bis(trimethyldecyl)decylamine (TMSA) ligands. The other manganese precursor contains two TMSA ligands and two pyridine (py) ligands and is referred to as a "stabilized" precursor. An example of a non-induced steel is a conventional ampule, which is usually provided with a non-induced steel lining. An example with SiO ₂ simulates a lining with lining. The percentage of non-volatile residue indicates the amount of precursor lost due to reaction with the surface. That is, the higher the percentage of non-volatile residues, the more the precursor losses. Therefore a lower percentage is required.

Figure 2 is a graph showing the percentage of non-volatile residues over a 18-day period, including trend lines based on data points. The 1A example (this example contains Mn(TMSA) ₂ in a heated stainless steel vessel) provides a baseline process because the vessel does not contain a liner and the precursor does not contain additional stabilizing ligands. Therefore, the 1A example is also used as a baseline for comparison with other examples. As can be seen from this figure, by day 18, there were approximately 17% non-volatile residues. In contrast, the addition of a liner container (Example 1B) with the same precursor showed only about 7% of non-volatile residue, which was equivalent to a drop of more than half. The 1C example (which is characterized by a stabilized precursor in a stainless steel vessel) is performed in a manner comparable to the unstable precursor in the liner-added vessel of the first example B. That is, after 18 days, the 1C example showed about 7.5% non-volatile residue, which was also less than half as shown in the Example 1A. The 1D example (which is characterized by both stabilized precursors and liner-added containers) shows the best results. After 18 days, the inference of the data of the 1D example shows that the percentage (%) of non-volatile residues is expected to be about 3.5%, which is lower than the 1B and 1C examples, and significantly lower than the 1A example. It is apparent from these examples that the advantages of stabilizing the precursor and/or adding a liner to the ampoule are evident.

Second instance

According to the following table, the Mn(TMSA) ₂ precursor was placed in several containers with different liners, and the Mn(TMSA) ₂ precursor was heated to a temperature of 90 ° C, and the temperature was maintained for 20 days:

Dursan ^TM and silcolloy ^TM representatives of two different silicon based anti-corrosion coating to the stainless steel tag. The labels and samples are included in a glass container (same as the Example 2A) and these labels will simulate the addition of a lined SST ampule by placing Mn(TMSA) ₂ in contact with the coated stainless steel. The heating vessel simulates the conditions under which the ampoules are heated. The percentage of non-volatile residue was measured for each sample at different time intervals. Figure 3 is a graph showing the percentage of non-volatile residues over a 20-day period, including the trend line for those data points. As shown in the figure, a variety of containers with metal oxide liners greatly reduce the percentage of non-volatile residues.

Third example (control example)

Figure 4 is a thermogravimetric analysis curve for Mn(TMSA) ₂ , and the derivative of the curve. The weight of the precursor was measured as a function of temperature. A small amount of precursor stabilized at 2 ° C / min. The solid curve represents the weight and the dashed curve represents the time derivative of the weight to provide a rate of mass loss (i.e., vaporization) at a given temperature.

Fourth instance

The fourth example was repeated for the test of the third example except that the precursor was Mn(TMSA) ₂ (py) ₂ (Mn(TMSA) ₂ (py) ₂ was regarded as a stabilizing precursor). Again, the solid curve represents the weight and the dashed curve represents the derivative of the weight to provide a rate of mass loss (i.e., vaporization) at a given temperature. Figure 5 illustrates the thermogravimetric analysis curve and the derivative of the thermogravimetric analysis curve. As can be seen from this figure, the stabilized precursor with a pyridine ligand has increased stability compared to Mn(TMSA) ₂ .

Fifth instance

The fifth example was repeated for the test of the third example except that the precursor was Mn(TMSA) ₂ (TMEDA) ₂ (the Mn(TMSA) ₂ (TMEDA) ₂ was regarded as a stabilizing precursor). Again, the solid curve represents the weight and the dashed curve represents the derivative of the weight to provide a rate of mass loss (i.e., vaporization) at a given temperature. Figure 6 illustrates the thermogravimetric analysis curve and the derivative of the thermogravimetric analysis curve. As can be seen from this figure, the stabilized precursor has increased stability compared to Mn(TMSA) ₂ . In addition, the TMEDA stabilized precursor does not have any significant volatility loss compared to Mn(TMSA) ₂ . Although the vertices illustrated by the derivative curve may mean some decomposition at their temperatures, the fact that the mass curve reaches zero means that the product of the decomposition is still volatile and may be acceptable.

300‧‧‧ source cans

302‧‧‧ Carrier gas source

306‧‧‧Processing chamber

312‧‧‧ valve

314‧‧‧ valve

402‧‧‧Cylindrical side wall

404‧‧‧ Cover

406‧‧‧Intake 埠

408‧‧‧Exhaust gas

410‧‧ ‧ baffle

414‧‧‧Precursor materials

416‧‧‧Liquid

418‧‧‧ upper area

420‧‧‧ Shell

422‧‧‧Intake pipe

424‧‧‧ first end

426‧‧‧ second end

430‧‧‧Resistive heater

432‧‧‧ bottom

436A‧‧‧Disconnected parts

436B‧‧‧Disconnecting accessories

438‧‧‧ internal volume

444‧‧‧ lining

450‧‧‧ oil collector

452‧‧‧ oil collector body

454‧‧ ‧ baffle

456‧‧‧ center line

Claims (20)

An apparatus for generating a chemical precursor gas, the apparatus comprising: a can having a side wall, a top end and a bottom, the side wall, the top end and the bottom forming an internal volume; an intake port and a The gas inlet port and the gas outlet port are in fluid communication with the inner volume; a liner, the liner being on at least a portion of the side wall, the top end or the bottom portion, wherein the liner comprises an inert metal oxide; and a precursor, The precursor is in the internal volume of the can, wherein the precursor contains at least one Mn-N bond and a 2-electron donor ligand. The apparatus of claim 1 wherein the liner is on at least a portion of the bottom. The device of claim 1 wherein the inert metal oxide comprises a dielectric. The apparatus of claim 1, wherein the inert metal oxide comprises SiO ₂ , Al ₂ O ₃ , TiO ₂ , lanthanum carbide, lanthanum oxychloride or Ta ₂ O ₅ . The apparatus of claim 1, wherein the 2-electron donor ligand comprises pyridine, tetrahydrofuran or tetrahydrothiophene, tetramethylethylenediamine, acetonitrile, tertiary amine or 2,2'-bipyridine. The device of claim 5, wherein the precursor has a structure, the structure being represented as: A method of depositing a manganese-containing film, the method comprising the steps of: providing a precursor comprising at least one Mn-N bond; and flowing the precursor through a device for generating a chemical precursor gas, wherein The device has a lining comprising a layer of an inert metal oxide. The method of claim 7, wherein the inert metal oxide comprises a dielectric. The method of claim 7, wherein the inert metal oxide comprises SiO ₂ , Al ₂ O ₃ , TiO ₂ , lanthanum carbide, lanthanum oxyhydroxide or Ta ₂ O ₅ . The method of claim 7, wherein the precursor has a structure, the structure being represented as: Wherein each A is independently selected from carbon or hydrazine, and each R is independently selected from hydrogen, methyl, substituted or unsubstituted alkane, branched or unbranched alkane, substituted or unsubstituted olefin, branched or non- Branched olefins, substituted or unsubstituted alkynes, branched or unbranched alkynes or substituted or unsubstituted aromatics. The method of claim 10, wherein each A is 矽. The method of claim 10, wherein each R group is a methyl group. The method of claim 10, wherein the precursor comprises bis(bistrimethyldecyl)guanamine manganese. The method of item 12 request, the method further comprising the steps of: exposing a substrate surface to the bis (bis trimethyl silicon alkyl) Amides NH ₃ contains one of manganese and second precursor. The method of claim 7, wherein the precursor further comprises a 2-electron donor ligand. The method of claim 15, wherein the 2-electron donor ligand comprises Pyridine, tetrahydrofuran or tetrahydrothiophene, tetramethylethylenediamine, acetonitrile, tertiary amine or 2,2'-bipyridine. The method of claim 15, wherein at least the Mn-N bond is part of the 2-electron donor complex. The method of claim 17, wherein the precursor has a structure, the structure being represented as: The method of claim 7, wherein the method further comprises the step of exposing a substrate surface to the precursor. A method of depositing a manganese-containing film, the method comprising the steps of: exposing a substrate surface to the vaporized precursor, wherein the precursor comprises: